0 Copyright 1992
Volume 1 1 , Number 7 , Ju& 1992
American Chemical Society
Communzcatzons Organometalllc Macrocycle Chemlstry. 2. Synthesls of Organometallic (Trlthlacyclononane)ruthenlum( I I) Complexes Jason Cannadine, Andrew Hector, and Anthony
F. Hill'
Depattment of Chemistry, Imperial Colbge, London SW7 2AY, U.K. Received December 20, 1991
Summary: The reactions of 1,4,7-trithlacyclononane(953) whh the coordlnathrely unsaturated a-vlnyl complexes [ R u ( C ~ H R ) C Y C O X W & ] (R = H, C4H9, C & M d ) proceed with loss of a chloride and a phosphine llgand from the coordination sphere to provide the salts [Ru(CR--c=HR~CoxPPh3K9-S3)]Cl (isdeteed as ASF6- Salts) in high yleld. Simllar treatment of the complex [Ru(C,H4Me-4)C(CO)(m)2] leads to the related a-tolyl derlvatke [RU(C,H,Me-4XCoxPPh3x9-S3)] CI. The anaiogous reactions of 9 4 3 with the related thiocarbonyl complexes [Ru(CR=CHPh)Cl(CS)(PPh3)2] (R = H, Ph) and [ R U ( C ( C ~ N ~ N M C S M P Pp r~o~w) the ~ I cationlc complexes [Ru(q2-SCCR=CHRXPPh3)(9-S3)] + and [R u ( C ( C ~ ~ ) ? = H C O , M ~ ) ( C S X P ~ ~ X+, ~ -the S~)] former vie vinyCthiocarbonyl ligand coupling.
The chemistry of polythia macrocycles, the sulfur analogues of crown ethers, has been primarily preoccupied with complexes bearing typically " c e n t " ligands, e.g., halides, carbonyls, $-Can groups, etc.' We are currently attempting to develop the organometallic chemistry of complexes bearing 1,4,7-trithiacyclononane(9433) ligands, in part to investigate the analogy between 9-53, cyclopentadienyl, $-arene, and ~ - H B ( P z(pz ) ~ = pyrazol-1-yl) ligands (Chart I). We report herein the simple synthesis of a class of u-vinyl and a-aryl complexes of ruthenium(II), bearing carbonyl or thiocarbonyl ligands. The 16-electron u-(E)-vinyl complexes [Ru(CH= CHR)Cl(CO)(PPh&,](R = H, C & , C&4Me-4)2react with
Chart I. Six-Electron Pac Ligands H
M
M+
Scheme I. Reactions of Ruthenium Phosphine Complexes with 9-83 (R = C6€14Me,CE--CBph,CPh4HPh)
IL
0
I
d
9-53 in dichloromethane solution with displacement of one phosphine and the chloride ligand. The aalta [Ru(CH= CH€€)(CO)(PPhJ(853)]Cl(R= H (l),C4H, (2), C a M e - 4 (3)) are formed in essentially quantitative yield and may be metathesized with sodium hexafluoroarsenate to provide the h F 6 derivatives. The grow formulation follows from the appearance of molecular ions in the FAB mass (2) Torres, M.R.;Vegas, A.; Santos, A. J. Organomet. Chem. 1986,
(1) Cooper, S.; Rawle, S. C. Struct. Bonding ISSO, 72, 1.
309, 169.
Q216-1333/92/2311-2323$03.oo/o (8 1992 American Chemical Society
Communications
2324 Organometallics, Vol. 11, No. 7, 1992 Scheme XI. Reactions of Ruthenium Thiocarbonyl Complexes with 9-83
+943
I
1
1
R=R
R = Ph R = H,Ph
t
= CO ~ M c
t
spectra of the complexes. The spectroscopic data for the complexes3 feature single carbonyl-associated infrared absorbances in the region 1960-1980 cm-l, while the trans @-vinylgroup is evident from the appearance of AB quartets in the 'H NMR spectra of the derivatives 2 and 3. COSY and NOE lH NMR experiments on [Ru(CH= CHC&Me-4)(CO)(PPhJ(9-S3)]Cl show that the molecule is static on the 'H NMR time scale. The a-aryl derivative (3) Data for ~Ru(CH=CHCBH4Me-4)(CO)(PPhs)(9-S3)]AsFs: IR (Nujol) 1970 cm- (um); 'H NMR (CDC13, 25 "C) 1.70, 2.10, 1.59, 2.82, 2.92, 2.96, 3.13 [m X 7, 12 H, 9-53], 2.27 [e, 3 H, C6H4CH3],6.96, 6.78 [(AB)z, 4 H, C&CH3, J(AB) 8.0 Hz], 6.54, 7.29 [AB, 1 H, PZRucHA=C~&,Ji4Me, J(AB) = 16.0, J = (PHA)= 16.8 Hz], 7.40-7.51 NMR (CDC13, 25 "C) 40.6 ppm; FAB-MS ppm [m, 15 H,P C a 1; (nba) m / e 689 (M'), 515 ([M - (9-S3)]+). Anal. Calcd for C3,HSqAeF&OPRu: C, 49.8; H, 4.1. Found C, 49.9; H. 4.1. Data for [Ru(q -SCCH=CHC$15)(PPh3)(9-S3)]C104: IR (Nujol) 1585 8, 1566 s cm-' (vinyl); 'H NMR (CDCl,, 25 "C) 1.03, 1.44,2.15, 2.26, 2.51,2.59 [m X 6, 1 H X 6,9-53],2.84,3.09 [m X 2,6 H, 9-53], 7.1B-7.54 ppm [m, 15 H, PC& and CC&]; FAB-MS m / e 691 (M+) (no significant fragmenC, 48.3; H, 4.2. tation). Anal. Calcd for CssHuC104PRuS4.0.5CHzClz: Found C, 47.9; H, 4.1. Data for [Ru(C(COzMe)=CHCOzMe)(CS)(PPh3)(9-S3)]C104: Et (Nujol) 1724 8 , 1714 sh (COzMe), 1570 (vinyl), 1290 VE (CS); 'H N M R (CDCla,25 "C) 2.09,2.27 [m X 2 , l H X 2,9-S3], 2.82,3.19,3.35 [m X 3 , l O H, 9-S3],3.51,3.75 [a X 2,6 H, COzCH3],5.38 [e (br), 1 H, =CHC02Me], 7.37-7.53 ppm [m, 15 H, PC&]; FAB-MS (nba) m / e 731 (M+) (no significant fragmentation). Anal. Calcd for CzeHuCIO&'RuS.2CHzClz: C, 43.3; H, 4.0. Found: C, 43.6; H, 3.9.
[Ru(C6H4Me4)(CO)(PPh3)(9-S3)]C1 (4) is readily prepared from the corresponding tolyl complex [Ru(C6H,Me-4)Cl(CO)(PPh3),] t and spectroscopicdata3 indicate that it is isoetructural with the vinyl derivatives. The thiocarbonyl ligand shows an enhanced propensity to enter into migratory insertion reactions, relative to coordinated C0.b The reactions of the recently prepared thiocarbonyl complexes [Ru(CR==CHR)Cl(CS)(PPhJ2] (R = H, Ph) and [RU{C(CO~M~)=CHCO~M~K~(CS)(PP~J~ were therefore of interest. Treating these complexes with 9-53 in the presence of LiC104 leads to formation of the purple thiocinnamoyl complexes [Ru(v2-SCCR=CHR)(PPh3)(9-S3)]+ or the yellow a-vinyl species [Ru(C(C02Me)=CHC02Me)(CS)(PPh3)(9-S3)]+ (Scheme 11). The observation of a migratory insertion coupling in the former complexes is unusual in that ancillary r-acid ligands are normally required for such a reaction to occur;s e.g., reaction of [RU(CH=CHP~)C~(CS)(PP~~)~] with sodium dimethyldithiocarbamate fails to induce such a reaction, providing rather the octahedral a-vinyl complex [Ru(CH=CHPh)(S2CNMe2)(CS)(PPh3)2].6 The failure of [Ru{C(C02Me)=CHC02Me)(CS)(PPh3)(9-S3)]+ to isomerize to the thioacyl tautomer presumably reflects enhanced Ru-C bond strength for the vinyl ligand. We are currently investigating the reactivity of these complexes in parallel studies of the related neutral hydrotris(pyrazoly1)borato derivatives [RuR(CO)(PPh3)(HB(pz),)] (pz = pyrazol-1-yl).' Consistent with the cationic nature of the 9 4 3 derivatives, the carbonyl stretching frequencies for the compounds appear ca. 30 cm-' to higher energy and the 'H chemical shifts of the vinylic protons (RuCR=CHR) are moved ca. 1 ppm to lower field of those observed for the hydrotris(pyraz01yl)borato analogues. Acknowledgment. We are grateful to Professor W. R. Roper and the University of Auckland Department of Chemistry for helpful discussions and the generous provision of research facilities. We wish to thank JohnsonMatthey Chemicalsfor a generous loan of ruthenium salts. OM910786X (4) Roper, W. R.; Wright, L. J. J. Organomet Chem. 1977, 142, C1. (5) Clark, G. R.; Collins, T. J.; Mareden, K.; Roper, W. R. J. Organomet. Chem. 1978,157, C23. Collins, T. J.; Roper, W. R. J. Organomet. Chem. 1977,139, C56. Elliott, G. P.; Roper, W. R. J. Organomet. Chem. 1986,250, C5. For a recent review of metal thiocarbonyl chemistry, see: Broadhuret, P. V. Polyhedron 1986,4,1801. (6) Hill, A. F.; Roper, W. R. To be submitted for publication in Organometallics. (7) Hill, A. F. J . Organomet. Chem. 1990, 395, C35. Alcock, N. W.; Hill, A. F.; Melling, R. P. Organometallics 1991, 10, 3898.
